High-strength high-hardness high-density arsenic-based alloy and preparation method thereof

Abstract

The application provides a high-strength, high-hardness and high-density arsenic-based alloy and a preparation method thereof. The preparation method comprises the following steps: S1, providing a mixture of arsenic-iron mixed powder and exogenous metal powder; the arsenic-iron mixed powder comprises arsenic powder and iron powder, and the exogenous metal powder comprises at least one of cobalt powder and manganese powder; the mass percentage of the exogenous metal powder and the arsenic-iron mixed powder is 3-25%; the molar ratio of the arsenic powder and the iron powder is 0.1-2:1; S2, ball milling the mixture under the protection of an inert atmosphere to obtain a ball milling product; and S3, vacuum hot-press sintering the ball milling product to obtain the arsenic-based alloy. By introducing specific exogenous metal powder, the strength, hardness and density of the arsenic-based alloy can be improved, the consumption way of arsenic resources is expanded, and the resources are realized and high-valued.

Description

Technical Field

[0001] This invention belongs to the field of arsenic-based alloy technology and high-value utilization, and particularly relates to a high-strength, high-hardness, and high-density arsenic-based alloy and its preparation method. Background Technology

[0002] Arsenic is both a pollutant and a resource. For example, high-purity arsenic is not only a raw material for producing compound semiconductors such as gallium arsenide and indium arsenide, and is widely used in microelectronics, optoelectronics, and other fields, but it is also widely used in the manufacture of diodes, light-emitting diodes, and lasers, although the arsenic doping level is relatively low. In the field of superconducting / magnetic materials, arsenic is used as an element in solid-state reactions to obtain bulk multi-element alloy materials. In emerging As-V group materials (SbAs, TaAs, NbAs) and group III-V compounds (BAs, TlAs), chemical vapor transport methods are often used for crystal growth to obtain high-purity single-crystal materials. However, these new functional materials are currently only in the basic research and exploratory application stage in the laboratory, and the preparation process has great difficulties and uncertainties, resulting in their non-practical application in the market.

[0003] To effectively utilize arsenic resources and expand arsenic resource utilization pathways, Chinese invention patent CN115491534B (the applicant's previous application) discloses an arsenic-iron alloy, its preparation method, and its resource utilization treatment method. Although it uses arsenic powder and iron powder to prepare the arsenic-iron alloy, its hardness only reaches a maximum of 899.41 HV0.5; and when the arsenic content is high, the density of the arsenic-iron alloy is low, and its compressive strength needs further improvement.

[0004] Therefore, it is necessary to provide a high-strength, high-hardness, and high-density arsenic-based alloy and its preparation method to solve or at least alleviate the technical defects of existing arsenic-based alloys that require further improvement in strength, hardness, and density. Summary of the Invention

[0005] The main objective of this invention is to provide a high-strength, high-hardness, and high-density arsenic-based alloy and its preparation method, aiming to solve or at least alleviate the technical problem that the strength, hardness, and density of existing arsenic-based alloys need to be further improved.

[0006] To achieve the above objectives, the present invention provides a method for preparing a high-strength, high-hardness, high-density arsenic-based alloy, comprising the following steps:

[0007] S1, providing a mixture of arsenic-iron mixed powder and exogenous metal powder; wherein the arsenic-iron mixed powder comprises arsenic powder and iron powder, and the exogenous metal powder comprises at least one of cobalt powder and manganese powder;

[0008] The mass percentage of the exogenous metal powder and the arsenic-iron mixed powder is 3-25%; the molar ratio of the arsenic powder to the iron powder is 0.1-2:1.

[0009] S2, Under the protection of an inert atmosphere, the mixture is ball-milled to obtain a ball-milled product; the ball milling speed is 250-400 r / min, and the ball milling time is 8-48 h;

[0010] S3, the ball-milled product is subjected to vacuum hot pressing sintering to obtain the arsenic-based alloy;

[0011] The vacuum hot pressing sintering includes:

[0012] The ball-milled product is placed in a vacuum environment; then, the ball-milled product is sintered, and during the sintering process, a pressure of 25 to 50 MPa is applied to the ball-milled product.

[0013] The sintering process includes:

[0014] The ball-milled product is heated to 350–500°C and held at that temperature for 0.3–1 hour; then, the ball-milled product is heated to 600–850°C and held at that temperature for 0.5–1.5 hours.

[0015] Furthermore, the exogenous metal powder includes cobalt powder, and the mass percentage of the cobalt powder and the arsenic-iron mixed powder is 3-25%.

[0016] Furthermore, the mass percentage of the cobalt powder and the arsenic-iron mixed powder is 14-21%.

[0017] Furthermore, the exogenous metal powder includes manganese powder, and the mass percentage of the manganese powder and the arsenic-iron mixed powder is 3-25%, 4-16%, or 4-6%.

[0018] Furthermore, the molar ratio of the arsenic powder to the iron powder is 0.1–0.35:1 or 0.35–2:1.

[0019] Furthermore, the ball-to-material ratio of the ball mill is 10 to 20:1; the grinding ball particle size used in the ball mill includes one or more of 3 mm, 6 mm, 10 mm and 15 mm.

[0020] Furthermore, during the ball milling process, the machine operates continuously for 20–60 minutes and then pauses for 3–15 minutes.

[0021] Furthermore, the arsenic powder can be sourced from arsenic slag.

[0022] The present invention also provides a high-strength, high-hardness, high-density arsenic-based alloy, which is prepared by any of the preparation methods described above.

[0023] Furthermore, the phases in the arsenic-based alloy include Fe, Co, FeAs, and CoAs.

[0024] Compared with the prior art, the present invention has at least the following advantages:

[0025] 1. This invention only requires the addition of exogenous metal powders such as cobalt powder before ball milling, with a mass ratio of 3 to 25 wt.%, making the operation simple.

[0026] 2. This invention can alloy arsenic, and the resulting arsenic-based alloy has a high degree of crystallinity.

[0027] 3. The arsenic-based alloy obtained by this invention has high strength, high hardness, and high density; in this invention, the arsenic-based alloy has a compressive strength higher than 1200 MPa at room temperature, a Vickers hardness of up to 1010.97 HV0.5, and a density of up to 7.9586 g / cm³. 3 It has unexpected technical effects.

[0028] 4. Based on the above properties, it is expected that arsenic can be effectively utilized and its value enhanced, expanding the pathways for arsenic resource disposal. This would effectively reduce the cost for enterprises to process arsenic slag and iron slag, and it is also expected that arsenic slag can be processed into arsenic products for sale and application, thereby improving the economic efficiency of arsenic slag and iron slag. For example, based on the high strength, high hardness, and high density properties of the arsenic-iron alloy of this invention, it is expected to be used as a high-end alloy. Attached Figure Description

[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0030] Figure 1 This is the BSE-Mapping diagram of the arsenic-based alloy in Example 1 of the present invention;

[0031] Figure 2 This is the BSE-Mapping diagram of the arsenic-based alloy in Example 2 of the present invention;

[0032] Figure 3 This is the BSE-Mapping diagram of the arsenic-based alloy in Example 3 of the present invention;

[0033] Figure 4 This is the BSE-Mapping diagram of the arsenic-based alloy in Example 4 of the present invention;

[0034] Figure 5This is the BSE-Mapping diagram of the arsenic-based alloy in Example 5 of the present invention;

[0035] Figure 6 This is the BSE-Mapping diagram of the arsenic-based alloy in Example 6 of the present invention;

[0036] Figure 7 This is the BSE-Mapping diagram of the arsenic-based alloy in Example 7 of the present invention;

[0037] Figure 8 This is the BSE-Mapping diagram of the arsenic-based alloy in Example 8 of the present invention;

[0038] Figure 9 The image shown is the XRD pattern of the arsenic-based alloy in Example 4 of this invention.

[0039] Figure 10 The image shown is the XRD pattern of the arsenic-based alloy in Example 8 of this invention.

[0040] Figure 11 This is a photograph of the arsenic-based alloy after partial polishing in Example 4 of the present invention.

[0041] Figure 12 This is a photograph of the arsenic-based alloy in Example 8 of the present invention after partial polishing.

[0042] Figure 13 This is a comparison chart of the compressive strength of the arsenic-based alloys in Examples 1-8 of this invention;

[0043] Figure 14 This is a density comparison chart of the arsenic-based alloys in Examples 1-8 of the present invention;

[0044] Figure 15 This is a comparison chart of the Vickers hardness of the arsenic-based alloys in Examples 1-8 of this invention.

[0045] The realization of the objective, functional characteristics and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0046] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0047] Furthermore, the technical solutions of the various embodiments of the present invention can be combined with each other, but only if they are based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention.

[0048] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention, as well as the prior art known to those skilled in the art and the description of this invention, may be implemented using any prior art methods, devices, and materials similar to or equivalent to those described, used, or made of materials in the embodiments of this invention.

[0049] This invention provides a method for preparing a high-strength, high-hardness, high-density arsenic-based alloy, comprising the following steps:

[0050] S1 provides a mixture of arsenic-iron mixed powder and exogenous metal powder, wherein the arsenic-iron mixed powder includes arsenic powder and iron powder, specifically it may be composed of arsenic powder and iron powder.

[0051] The molar ratio of arsenic powder to iron powder is 0.1 to 2:1 (the molar ratio of arsenic in arsenic powder to iron in iron powder); specifically, the molar ratio of arsenic powder to iron powder can be 0.1 to 0.35:1 or 0.35 to 2:1.

[0052] To ensure the purity of each metal powder, the purity of the cobalt powder, the iron powder, and the arsenic powder can all be no less than 98.0 wt.%.

[0053] In order to achieve the resource utilization and high-value treatment of solid waste, the metal powders in this invention can be derived from corresponding metal waste residues; for example, the arsenic powder can be derived from arsenic slag.

[0054] To improve the performance of arsenic-based alloys, this invention introduces exogenous metal powder, wherein the mass percentage of the exogenous metal powder and the arsenic-iron mixed powder is 3-25%, and more preferably 5-20%.

[0055] In this invention, the exogenous metal powder includes or is at least one of cobalt powder and manganese powder.

[0056] Preferably, the exogenous metal powder includes or is cobalt powder, and the mass percentage of the cobalt powder and the arsenic-iron mixed powder is 3-25% or 14-21%, or the mass percentage of the cobalt powder and the arsenic-iron mixed powder may also be 5-20% or 15-20%. Alternatively, the exogenous metal powder includes or is manganese powder, and the mass percentage of the manganese powder and the arsenic-iron mixed powder may be 3-25% or 4-16% or 4-6%, or the mass percentage of the manganese powder and the arsenic-iron mixed powder may also be 5-20% or 5-15% or 5%.

[0057] When the exogenous metal is manganese powder, it can improve the compressive strength of the alloy to a certain extent; when the mass percentage of the exogenous metal powder and the arsenic-iron mixed powder is 4-16%, it can improve the density of the alloy to a certain extent; when the mass percentage of the exogenous metal powder and the arsenic-iron mixed powder is 4-6%, it can improve the hardness of the alloy to a certain extent.

[0058] It should be noted that, compared to manganese powder, limiting the exogenous metal powder to cobalt powder can comprehensively improve the performance of arsenic-based alloys, resulting in unexpected technical effects. Furthermore, when the mass percentage of the exogenous metal powder and the arsenic-iron mixed powder is 14-21%, the strength, density, and hardness of the arsenic-based alloy can be significantly improved, thereby solving the technical problems faced by this application.

[0059] S2, under the protection of an inert atmosphere, the mixture is ball-milled to carry out a mechanical alloying reaction, yielding a ball-milled product.

[0060] In this invention, the rotation speed of the ball mill is 250-400 r / min, the ball milling time is 8-48 h, and the ball milling time includes the pause time; specifically, the ball-to-material ratio of the ball mill can be 10-20:1; the particle size of the grinding balls used in the ball mill can be one or more of 3 mm, 6 mm, 10 mm and 15 mm.

[0061] During the ball milling process, the machine is continuously operated for 20 to 60 minutes and then paused for 3 to 15 minutes.

[0062] The vacuum ball mill jar used in this invention has an inner lining material of stainless steel, corundum, or cemented carbide; the grinding balls can also be made of stainless steel, corundum, or cemented carbide. In this invention, the inert gas may include at least one of argon and nitrogen.

[0063] S3, the ball-milled product is subjected to vacuum hot pressing sintering to obtain the arsenic-based alloy.

[0064] The vacuum hot pressing sintering includes:

[0065] The ball-milled product is placed in a vacuum environment; then, the ball-milled product is sintered, and during the sintering process, a pressure of 25 to 50 MPa is applied to the ball-milled product.

[0066] The sintering process includes:

[0067] The ball-milled product is heated to 350–500°C and held at that temperature for 0.3–1 hour; then, the ball-milled product is heated to 600–850°C and held at that temperature for 0.5–1.5 hours.

[0068] The vacuum hot pressing process can be understood as follows: First, a vacuum is evacuated for 10–20 minutes; after evacuation, the temperature is raised from room temperature to 350–500℃ and held for 0.3–1 hour; then the temperature is raised to 600–850℃ and held for 0.5–1.5 hours; afterwards, the furnace is cooled to room temperature. During sintering, the pressure is raised to 25–50 MPa; afterwards, the furnace is cooled to chamber pressure.

[0069] The present invention also provides a high-strength, high-hardness, high-density arsenic-based alloy, which is prepared by any of the preparation methods described above.

[0070] Based on the technical role of cobalt powder in this application, the phases in the arsenic-based alloy include Fe, Co, FeAs, and CoAs, thereby ensuring the performance of the arsenic-based alloy. The compressive strength of the arsenic-based alloy can reach 1157–1298 MPa, and the density can reach 7.7–8 g / cm³. 3 Its Vickers hardness can reach 955-1011 HV0.5.

[0071] The following are specific examples of the present invention:

[0072] The performance testing method used in this invention is as follows:

[0073] Density: The density of the samples in each embodiment was measured using the AKD-220A touch screen high-precision solid density tester and the Archimedes principle buoyancy method.

[0074] Compressive strength: tested using an electronic universal testing machine;

[0075] Hardness test: Vickers hardness tester was used.

[0076] Example 1

[0077] 1. Mix cobalt powder with a purity of 99 wt.%, iron powder with a purity of 99.5 wt.%, and arsenic powder with a purity of 98 wt.% to obtain a mixture (first mix arsenic powder and iron powder to obtain an arsenic-iron mixed powder, and then add cobalt powder to the arsenic-iron mixed powder); place the mixture into a vacuum ball mill jar, and the gas in the vacuum ball mill jar is argon.

[0078] The molar ratio of arsenic powder to iron powder is 0.6:0.4, and the mass percentage of cobalt powder and arsenic-iron mixed powder is 5% (that is, the amount of cobalt powder added is 5 wt.% of the total mass of arsenic-iron mixed powder).

[0079] 2. Place the above-mentioned vacuum ball mill jar on a high-energy planetary ball mill. The inner lining of the vacuum ball mill jar is made of stainless steel, and the grinding balls are made of stainless steel. The grinding balls are 6mm and 10mm grinding balls distributed in a 1:1 weight ratio, with a ball-to-material ratio of 20:1. The mechanical alloying reaction is carried out at a rotation speed of 340r / min. The reaction is continuously run for 30min and then paused for 5min. The reaction time is 40h (including the pause time). After the mechanical alloying reaction is completed, the sample (ball milling product) is taken out.

[0080] 3. Place the obtained sample (ball milling product) into the mold of the vacuum hot pressing sintering furnace and maintain the vacuum for 20 minutes to avoid the presence of oxygen.

[0081] Subsequently, the vacuum hot pressing sintering furnace was controlled to perform vacuum hot pressing sintering on the sample according to the following settings:

[0082] The temperature was increased to 400℃ at a rate of 10℃ / min and held for 30 min, then increased to 800℃ at a rate of 10℃ / min and held for 60 min, and finally cooled to room temperature in the furnace.

[0083] While controlling the temperature, the pressure was simultaneously increased to 30 MPa at a rate of 0.5 MPa / s and maintained for 160 minutes, and finally decreased to the room pressure at a rate of 0.5 MPa / s.

[0084] When the temperature is cooled to room temperature and the pressure is reduced to room pressure (no more pressure is applied), the arsenic-based alloy in this embodiment is obtained, namely the As-Fe-5Co alloy.

[0085] In this embodiment, the BSE-Mapping diagram of the arsenic-based alloy (As-Fe-5Co) bulk is shown below. Figure 1 As shown, the surface exhibits numerous pores of varying sizes. The alloy contains two phases: a dark gray phase and a grayish-white phase, with the dark gray phase being more predominant. This is presumably an intermediate phase formed from Fe and As. Based on the EDS analysis results in Table 1, the atomic ratio of As to Fe in the dark gray region (Spot 1) is close to 1:1, suggesting the presence of the FeAs phase. In the grayish-white region (Spot 2), the atomic ratio of As to Fe is close to 2:1, suggesting the presence of the FeAs2 phase. Furthermore, the mapping test results indicate that the elemental distribution in the alloy is not uniform, with obvious As-enriched regions.

[0086] In this embodiment, see Figure 13As shown, the compressive strength of the As-Fe-5Co alloy is 644.45 MPa.

[0087] In this embodiment, see Figure 14 As shown, the density of the As-Fe-5Co alloy is 7.4635 g / cm³. 3 .

[0088] In this embodiment, see Figure 15 As shown, the hardness of the As-Fe-5Co alloy is 912.72HV0.5.

[0089] Example 2

[0090] Compared to Example 1, this embodiment adjusts the amount of cobalt powder added so that the mass percentage of the cobalt powder and arsenic-iron mixed powder is 10%, while keeping other conditions unchanged, to obtain the arsenic-based alloy in this embodiment, namely the As-Fe-10Co alloy.

[0091] In this embodiment, the BSE-Mapping diagram of the As-Fe-10Co alloy is shown below. Figure 2 As shown, it can be seen that there are still pores of uneven size on the surface; the alloy also has two phases, one is dark gray and the other is grayish-white, and the proportion of grayish-white area is increasing; in addition, according to the mapping test results, it can be seen that the element-enriched areas in the alloy are reduced.

[0092] In this embodiment, see Figure 13 As shown, the compressive strength of the As-Fe-10Co alloy is 820.77 MPa, which is a further improvement compared to the As-Fe-5Co alloy.

[0093] In this embodiment, see Figure 14 As shown, the density of the As-Fe-10Co alloy is 7.6215 g / cm³. 3 Compared with the As-Fe-5Co alloy, its density is further improved.

[0094] In this embodiment, see Figure 15 As shown, the As-Fe-10Co alloy has a hardness of 906.7HV0.5, which is slightly lower than that of the As-Fe-5Co alloy.

[0095] Example 3

[0096] Compared to Example 1, this embodiment adjusts the amount of cobalt powder added so that the mass percentage of the cobalt powder and arsenic-iron mixed powder is 15%, while keeping other conditions unchanged, to obtain the arsenic-based alloy in this embodiment, namely the As-Fe-15Co alloy.

[0097] In this embodiment, the BSE-Mapping diagram of the As-Fe-15Co alloy is shown below. Figure 3 As shown, the number of pores has further decreased, and the regional distribution has gradually become more uniform, indicating that the alloy phase has become more homogeneous.

[0098] In this embodiment, see Figure 13 As shown, the compressive strength of the As-Fe-15Co alloy is 1157.75 MPa, which is significantly higher than that of the As-Fe-5Co alloy.

[0099] In this embodiment, see Figure 14 As shown, the density of the As-Fe-15Co alloy is 7.7607 g / cm³. 3 Compared with the As-Fe-5Co alloy, its density is further improved.

[0100] In this embodiment, see Figure 15 As shown, the As-Fe-15Co alloy has a hardness of 955.1HV0.5, which is an increase in hardness compared to the As-Fe-5Co alloy.

[0101] Example 4

[0102] Compared to Example 1, this embodiment adjusts the amount of cobalt powder added so that the mass percentage of the cobalt powder and arsenic-iron mixed powder is 20%, while keeping other conditions unchanged, to obtain the arsenic-based alloy in this embodiment, namely the As-Fe-20Co alloy.

[0103] In this embodiment, the BSE-Mapping diagram of the As-Fe-20Co alloy is shown below. Figure 4 As shown, the number of pores has been significantly reduced. Combined with the EDS energy dispersive spectroscopy analysis results, the As and Fe elements in the Spot 7 and Spot 8 spot scans are the same, indicating that the alloy elements are homogenized and there is no obvious regional difference, indicating that the phase is homogenized.

[0104] In this embodiment, the XRD analysis results of the As-Fe-20Co alloy are shown in [reference needed]. Figure 9 As shown, the main phases are iron and cobalt, with some FeAs signal peaks and low-density CoAs signal peaks, but no elemental As signal peaks were detected. This indicates that As was pre-alloyed first, and the alloy phase mainly exists in the form of an iron-cobalt solid solution. The solid solution content increases with the increase of cobalt mass fraction.

[0105] In this embodiment, the physical sample of the arsenic-based alloy is shown below. Figure 11 As shown, it can be demonstrated that alloy blocks can be prepared by mechanical alloying and vacuum hot pressing sintering after incorporating Co.

[0106] In this embodiment, see Figure 13 As shown, the compressive strength of the As-Fe-20Co alloy is 1297.78 MPa, which is twice that of the As-Fe-5Co alloy. This is likely due to solid solution strengthening.

[0107] In this embodiment, see Figure 14 As shown, the density of the As-Fe-20Co alloy reaches 7.9586 g / cm³ compared to the As-Fe-5Co alloy. 3 With further increases in density, this alloy can be considered a high-density alloy.

[0108] In this embodiment, see Figure 15 As shown, the As-Fe-20Co alloy has a hardness of 1010.97HV0.5, which is a further improvement in hardness compared to the As-Fe-5Co alloy.

[0109] Example 5

[0110] Compared to Example 1, in this embodiment, 99 wt.% of cobalt powder is replaced with 99 wt.% of manganese powder, while other conditions remain unchanged, resulting in the arsenic-based alloy of this embodiment, namely the As-Fe-5Mn alloy.

[0111] In this embodiment, the BSE-Mapping diagram of the As-Fe-5Mn alloy is shown below. Figure 5 As shown, a small number of relatively large pores exist. Combined with the EDS energy dispersive spectroscopy results in Table 2, the atomic ratio of As to Fe in both Region 1 (Spot 1) and Region 2 (Spot 2) is close to 2:1, suggesting a FeAs2 phase. Furthermore, according to the mapping test results, the Mn element distribution in this alloy is uneven, with obvious Mn-enriched regions.

[0112] In this embodiment, see Figure 13 As shown, the compressive strength of the As-Fe-5Mn alloy is 691.88 MPa.

[0113] In this embodiment, see Figure 14 As shown, the density of the As-Fe-5Mn alloy is 7.5083 g / cm³. 3 .

[0114] In this embodiment, see Figure 15 As shown, the As-Fe-5Mn alloy has a hardness of 918.45HV0.5, which is relatively high.

[0115] Example 6

[0116] Compared to Example 2, in this embodiment, 99 wt.% of cobalt powder is replaced with 99 wt.% of manganese powder, while other conditions remain unchanged, resulting in the arsenic-based alloy of this embodiment, namely the As-Fe-10Mn alloy.

[0117] In this embodiment, the BSE-Mapping diagram of the As-Fe-10Mn alloy is shown below. Figure 6 As shown, there is no obvious change in morphology. Compared with the As-Fe-5Mn alloy, the homogenization of the alloy phases is reduced, and a small number of other phases appear.

[0118] In this embodiment, see Figure 13 As shown, the compressive strength of the As-Fe-10Mn alloy is 821.37 MPa.

[0119] In this embodiment, see Figure 14 As shown, the density of the As-Fe-10Mn alloy is 7.4807 g / cm³. 3 Compared to the As-Fe-5Mn alloy, its density is reduced.

[0120] In this embodiment, see Figure 15 As shown, the As-Fe-10Mn alloy has a hardness of 854.97HV0.5, which is lower than that of the As-Fe-5Mn alloy.

[0121] Example 7

[0122] Compared to Example 3, in this embodiment, 99 wt.% of cobalt powder is replaced with 99 wt.% of manganese powder, while other conditions remain unchanged, resulting in the arsenic-based alloy of this embodiment, namely the As-Fe-15Mn alloy.

[0123] In this embodiment, the BSE-Mapping diagram of the arsenic-based alloy is shown below. Figure 7 As shown, the morphology and phase composition of the alloy are not significantly different from those of the As-Fe-10Mn alloy.

[0124] In this embodiment, see Figure 13 As shown, the compressive strength of the As-Fe-15Mn alloy is 885.22 MPa.

[0125] In this embodiment, see Figure 14 As shown, the density of the As-Fe-15Mn alloy is 7.5023 g / cm³. 3 Compared to the As-Fe-5Mn alloy, its density is reduced.

[0126] In this embodiment, see Figure 15As shown, the As-Fe-15Mn alloy has a hardness of 855.78HV0.5, which is lower than that of the As-Fe-5Mn alloy.

[0127] Example 8

[0128] Compared to Example 4, in this embodiment, 99 wt.% of cobalt powder is replaced with 99 wt.% of manganese powder, while other conditions remain unchanged, resulting in the arsenic-based alloy of this embodiment, namely the As-Fe-20Mn alloy.

[0129] In this embodiment, the BSE-Mapping diagram of the arsenic-based alloy is shown below. Figure 8 As shown, significant changes in morphology and phase can be observed. Combined with the EDS energy dispersive spectroscopy results in Table 2, it can be seen that the Mn content in region 7 (Spot 7) is higher than that in region 8 (Spot 8), indicating a clear enrichment of Mn and an uneven elemental distribution.

[0130] In this embodiment, the XRD analysis results of the As-Fe-20Mn alloy are shown in [reference needed]. Figure 10 As shown, the main phase is a manganese-iron-arsenic mesophase Mn0.15Fe0.85As.

[0131] In this embodiment, the physical sample of the As-Fe-20Mn alloy is shown below. Figure 12 As shown, it can be seen that alloy blocks can be prepared by mechanical alloying and vacuum hot pressing sintering after incorporating Mn.

[0132] In this embodiment, see Figure 13 As shown, the compressive strength of the As-Fe-20Mn alloy is 752.86 MPa, which is significantly lower than the expected value.

[0133] In this embodiment, see Figure 14 As shown, the density of the As-Fe-20Mn alloy is 7.3202 g / cm³. 3 Compared to the As-Fe-5Mn alloy, its density is reduced.

[0134] In this embodiment, see Figure 15 As shown, the As-Fe-20Mn alloy has a hardness of 791.58HV0.5, which is lower than that of the As-Fe-5Mn alloy.

[0135] Analysis example 1

[0136] 1. Table 1 is Figures 1-4 EDS energy dispersive spectroscopy analysis results:

[0137] Table 1. EDS energy dispersive spectroscopy analysis (at.%) of As-Fe-xCo (x=5, 10, 15, 20 wt.%) alloy bulks

[0138]

[0139] 2. Table 2 is Figures 5-8 EDS energy dispersive spectroscopy analysis results:

[0140] Table 2. EDS energy dispersive spectroscopy analysis (at.%) of As-Fe-xMn alloy bulk materials (x = 5, 10, 15, 20 wt.%)

[0141]

[0142] Analysis example 2

[0143] Analysis of the compressive strength, density, and hardness test results showed that adding 20 wt.% cobalt powder resulted in optimal performance, with the prepared arsenic-based alloy (As-Fe-20Co) achieving a compressive strength of 1297.78 MPa and a density of 7.9586 g / cm³. 3 The Vickers hardness value reaches 1010.97HV0.5.

[0144] The increase in compressive strength may be attributed to the increase in solid solution content. Figure 1-4 It can be seen that as the mass ratio of cobalt powder increases, the phase distribution gradually becomes more uniform, which leads to an increase in compressive strength.

[0145] The increase in density can likely be attributed to the density of cobalt itself, with a theoretical density of 8.9 g / cm³. 3 However, given that the amount of manganese powder added is not positively correlated with density, it is speculated that the increase in density may also be affected by other factors.

[0146] The increase in hardness may be attributed to changes in the phase composition and the effect of uniform phase dispersion; from Figure 9 and Figure 10 It can be seen that the main phases of the As-Fe-20Mn alloy are Mn0.15Fe0.85As, while the main phases of the As-Fe-20Co alloy are FeAs and CoAs. Furthermore, the phase distribution of the As-Fe-20Co alloy is more uniform than that of the As-Fe-20Mn alloy, based on the mapping and EDS analysis results.

[0147] The above technical solutions of the present invention are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. All equivalent structural transformations made under the technical concept of the present invention using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are included in the patent protection scope of the present invention.

Claims

1. A method for preparing a high-strength, high-hardness, high-density arsenic-based alloy, characterized in that, Including the following steps: S1, providing a mixture of arsenic-iron mixed powder and exogenous metal powder; the arsenic-iron mixed powder includes arsenic powder and iron powder, and the exogenous metal powder includes cobalt powder; the amount of cobalt powder added is 14~21% of the total mass of the arsenic-iron mixed powder, and the molar ratio of arsenic powder to iron powder is 0.1~2:1; S2, Under the protection of an inert atmosphere, the mixture is ball-milled to obtain a ball-milled product; the ball milling speed is 250~400 r / min, and the ball milling time is 8~48 h; S3, the ball-milled product is subjected to vacuum hot-pressing sintering to obtain the arsenic-based alloy; the arsenic-based alloy has a compressive strength of 1157~1298 MPa and a density of 7.7~8 g / cm³. 3 Its Vickers hardness is 955~1011 HV0.5; The vacuum hot pressing sintering includes: The ball-milled product is placed in a vacuum environment; then, the ball-milled product is sintered, and during the sintering process, a pressure of 25-50 MPa is applied to the ball-milled product. The sintering process includes: The ball-milled product is heated to 350-500°C and held for 0.3-1 hour; then, the ball-milled product is heated to 600-850°C and held for 0.5-1.5 hours.

2. The preparation method according to claim 1, characterized in that, The molar ratio of the arsenic powder to the iron powder is 0.1~0.35:1 or 0.35~2:

1.

3. The preparation method according to claim 1, characterized in that, The ball-to-material ratio of the ball mill is 10-20:1; the grinding ball particle size used in the ball mill includes one or more of 3mm, 6mm, 10mm and 15mm.

4. The preparation method according to claim 1, characterized in that, During the ball milling process, the machine is continuously operated for 20-60 minutes and then paused for 3-15 minutes.

5. The preparation method according to claim 1, characterized in that, The arsenic powder is sourced from arsenic slag.

6. A high-strength, high-hardness, high-density arsenic-based alloy, characterized in that, It is prepared using the preparation method described in any one of claims 1-5.

7. The arsenic-based alloy according to claim 6, characterized in that, The phases in the arsenic-based alloy include Fe, Co, FeAs, and CoAs.

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